Biodegradable polymer adhesives, hybrids and anomaterials

498 Pages·2008·8.78 MB·English

by  Mylonakis, Andreas

“Biodegradable Polymer Adhesives, Hybrids and
Nanomaterials”

A Thesis
Submitted to the Faculty
of
Drexel University
by
Andreas Mylonakis
in partial fulfillment of the
requirements for the degree
of
Doctor of Philosophy
September 2008
i
© Copyright 2008
Andreas Mylonakis. All Rights Reserved.
ii
Dedications
This work is dedicated to my mom Loukia Tsoni, my brother Gewrgios Mylonakis, my
grandmother Gewrgia Tsoni and my fiancé Catherine Stoupas for their encouragement, support
and love. I would also like to dedicate it to Dr. Andreas Athinaios, the president of The Hellenic
Foundation, that supported me not only financially but also psychologically. I know that this work
makes them happy and proud.

iii
Acknowledgements
Throughout these years in Drexel University there are many people that I have become
thankful of, without whom most probably I would not be able to pursue my doctorate. First, I
would like to express my gratitude to my advisor Dr. Yen Wei for his guidance, support and help.
Amongst others, what I have learned from him and which will be followed throughout my
scientific career was to enjoy what I am doing, be open to new ideas and remain always challenged
by trying novel things. With his own unique way he kept me highly motivated, focused and
inspired to reach the final goal of pursuing something that will have a small or a big impact to
society. As he always keeps saying, chemistry is an art, and you need imagination to become a
good artist. I express my sincere appreciation to a big mentor for my scientific career and my
personal life.
Words are very little to describe my gratitude to The Hellenic Foundation, and Dr. Andreas
Athinaios in particular, for supporting me with a full-time scholarship to obtain the PhD in
Chemistry at Drexel University. His support, financial but more importantly psychological will be
always remembered and never taken for granted. He opened new highways for my scientific career
and personal life, and I am very glad to know that this thesis makes him and The Hellenic
Foundation very proud. On a personal level I’ve learned the virtues of patience, hard work,
integrity, and love, and which I will do my best to follow for the rest of my life. I will never forget
that he was always there for me with a non-stop effort to reach solutions to my problems, enjoy my
happy moments and support me in the bad days during my PhD years.
iv
I would also like to thank and express my appreciation to Dr. Shuxi Li who was always the
first resource of scientific guidance and information throughout this research work. I will always
remember his continuous efforts to organize the laboratory, to answer questions and seek solutions
to potential problems. Our great collaboration in many research projects will be always
remembered. I owe my sincere appreciation to Dr. Amar Nath from University of North Carolina
for his guidance and the great collaboration we had on the phthalocyanine research work. I would
especially like to thank Dr. David Soll, Dr. Jack Baldwin and Dr. Cyrial Evian for their guidance,
inspiration and great collaboration we had in the biodegradable adhesives I have worked on.
I want to thank my candidacy examination and/or my dissertation defense committee
members, Dr. Daniel King, Dr. Lynn Penn, Dr. Robert Hutchins, Dr. Sally Solomon, Dr. Jun Xi,
Dr. Shu Yang, Dr. Guoliang Yang and Dr. Jian-Min Yuan. Their time and valuable suggestions are
highly appreciated.
I would like to express my appreciation to Dr. Kevin Owens for training me on several
analytical instruments, all the professors in the department of Chemistry for being there for me,
and Drexel University for providing me with a great working environment. I also thank Dr.
Solomon Samuel who helped me with the mechanical testing of many of my research samples and
the good collaboration we had. I acknowledge Dr. Nadaraj Sundar Babu for his valuable help in
many of the projects. I thank Mrs. Dee Breger, Dr. Zhorro Nikolov, Dr. Edward Basgall, Dr. Boris
Polyak, Dr. Anat Katsir and Mrs. Leko Lin for training me on various microscopic and
spectroscopic instruments. I also want to thank Dr. Xing Geng and Dr. Giuseppe R. Palmese for
assisting and facilitating the usage of the instron instrument. I would like to express my
thankfullness to Mr. Edward Doherty, Mrs. Virginia Nesmith and Mrs. Edith Smith for their
v
assistance all these years. I would like to thank Mr. Thomas Cachaza for making many custom-
made apparatus.
I want to express my appreciation to many of the graduate students past and present who
have been there for me. Mrs. Widalys Gonzalez, Mrs. Laquisha Hamilton, Mr. Gordan Reeves,
Mrs. Guzeliya Korneva, Mrs. Adeline Kojtari, Mrs. April Holcomb, Dr. Hung Le, Mr. Thomas
Measey, Mr. Andrew Hagerman, Mr. Khalid Baig Mirza, Mrs. Stephanie Schuster, Mrs. Alma
Pipic, Mr. James Rieben, Mr. Matthew Rossi, Mrs. Renata Szyszka, Mrs. Kim Kahle, Mrs.
Mozhgan Bahadory, Mr. William Erb, …. the list goes on. Special thanks are due to all the past
and present associates and students in Dr. Wei’s lab, Dr. Zongtao Zhang, Dr. Houping Yin, Dr.
Zhengfei Sun, Dr. Alpa Patel, Dr. Yi Guo, Mr. Mathew Zagorski, Mr. Indraneil Mukherjee, Mr.
Somang Kim, Mr. Sudipto Das, Mr. David Berke-Schlessel, Mr. Kerry Drake, Mr. Charles
Bowman, Mr. Alexksander Fisher, Dr. Siui Li. I want to also express my gratitude to Mr. Colin
Murray and Mr. Tom Hughes for the valuable discussions and the financial help for the enzyme
work.
I want to express my gratefulness to my mom Loukia Tsoni who has always stood by my
side all these years with innumerable sacrifices and efforts to raise me and my brother with love,
integrity and self-esteem. I know that this work makes her very proud. I express my gratitude to
my brother and grandmother for their love and support. I also want to thank the most precious
thing in my life, my fiancé Catherine Stoupas, for her unconditional love, help and support through
these years.
vi
Table of contents
List of Tables……………………………………………...…………….….…………………..xvi
List of Schemes………………………………………...…………….….………...……….......xvii
List of Figures………………………………………..……….…………...……………….…....xx
List of Symbols……………………………………….......……………….…….......……...….xxvi
List of Abbreviations………………………………………...…………….………….…........xxvii
Abstract……………………………………………………….…………….……....................xxxv
Chapter 1:. Introduction to Polymers, Hybrid Materials and Nanomaterials
1.1 History and Motivation…………………………………………………………………...........1
1.2 Biodegradable Polymers……………………………………….………………………..….…..7
1.2.1 Classes of Biodegradable Polymers…………………….………………...…….....………9
1.2.2 Biodegradable Adhesives……………………………..………………….……...…...……9
1.3 Hybrid Materials..……………………………………………………………..………………11
1.3.1 Hybrids Prepared by the Sol-Gel Method…………….…...………….……………….....13
1.4 Conductive Polymers (CPs).…………………………………….………...……………….....14
1.5 Nanomaterials……………………………………………………………………………..…..16
1.6 Organization of this Dissertation……………………………………………………………...18
1.7 Reference List…………………………………………………………………………………25
Chapter 2. Introduction to the General Methodologies and Techniques Used
2.1 Introduction……………………………………………………………………………..…….31
2.2 Biodegradable Polymers…………………………………………………………………...….31
2.2.1 Biodegradable Adhesives…………………………………………….…………………...31
2.2.2 Characterization of the Synthesized Biodegradable Polymers………...….……………....33
2.2.2.1 Nuclear Magnetic Resonance Spectroscopy (NMR)………………...………………..33
2.2.2.2 IR Spectroscopy……………………………………………………..…………..……35
2.2.2.3 UV-Vis Spectroscopy………………………………………………..………….…….36
2.3 Hybrid Materials………………………………………………………………………………37
vii
2.3.1 Introduction……………...………………………………………………………………..37
2.3.2 Hybrid Materials by the Sol-Gel Method…………………………………………………37
2.3.3 Introduction to Sol-Gel Chemistry………………………………………………………..40
2.3.3.1 Precursors Used……………………………………………………………………….41
2.3.4 Characterization Techniques of the Hybrid Materials…………………………………....43
2.3.4.1 Mechanical Properties Measurements………………………………………………...43
2.3.4.2 Electroanalytical Methods…………………………………………………………….45
2.3.4.2.1 Cyclic Voltammetry………………………………………………………………47
2.3.4.2.2 Rotating Disk Polarography……………………………………………………....51
2.3.4.3 Conductimetry……………………….…………………….………..………………...52
2.4 Nanomaterials………………………………………………………………..………………..52
2.4.1 Characterization of Nanomaterials……………………………………….….……………53
2.4.1.1 Scanning Electron Microscope (SEM)………………………………..…….…………53
2.4.1.2 X-ray Diffraction (XRD)………………………………………………………………55
2.4.1.3 Gas Sorption Measurement…………………………………………..………………...55
2.5 Reference List………………………………………………………………………………….75
Chapter 3. A Biomimetic, Biodegradable, Biocompatible and Non-Toxic Adhesive
3.1 Introduction and Motivation……………………………………...……………………………81
3.1.1 Chitosan……………………………………………………………………………………82
3.1.2 Adhesive Proteins………………………………………………...………………………..84
3.2 Experimental Section…………………………………………………………………………..86
3.2.1 Materials……………………………………………………………..…………………….86
3.2.2 Synthesis Procedure…………………………………………………..……………………86
3.2.3 Instrumentation and Methods……………………………………………...………………89
3.2.3.1 Spectroscopic Methods…………………………………………………..…………….89
3.2.3.2 Mechanical Testing………………………………………………………….…………89
3.2.3.3 Degradation Studies…………………………………………………………...……….93
3.3 Results and Discussion…………………………………………………………………...……93
3.3.1 Synthesis and Characterization of Modified Chitosans……………………………………93
viii
3.3.2 1H-NMR Spectroscopy……………………………………...……………………………..93
3.3.3 FT-IR Spectroscopy………………………………………………..………………………95
3.3.4 Ultraviolet-Visible Spectroscopy (UV-vis)……………………………….……………….95
3.3.5 Mechanical Testing………………………………………………………….……………..96
3.3.5.1 Tensile Strength Tests………………………………………………………...………..96
3.3.5.2 Shear Strength Tests……………………………………………………………...…....99
3.3.6 Degradation Studies…………………………………………………………………..…..101
3.4 Several Considerations……………………………………………………………………......102
3.5 Conclusions…………………………………………………………………………………...103
3.6 Acknowledgements…………………………...………………………………………………103
3.7 Reference List………………………………………………...………………………………118
Chapter 4. Synthesis and Characterization of Novel Organic-Inorganic poly(HEMA-GMA-
silica) Hybrid Materials
4.1 Introduction and Motivation………………………………………………………………….123
4.2 General Methodology……………………………………………………………..………….126
4.3 Experimental Section…………………………………………………………………...…….129
4.3.1 Materials…………………………………………………………………………….……129
4.3.2 Methods…………………………………………………………………………….……..129
4.3.3 Thermal Properties…………………………………………………………………...…...129
4.3.4 Morphology…………………………………………………………………………….…130
4.3.5 Evaluation of Mechanical Properties……………………………………………………..130
4.3.6 Synthesis Procedure of PHGS (poly (HEMA-GMA-silica))……………………………..131
4.3.6.1 Hydrolysis of TEOS with HEMA………………………………...…………………..131
4.3.6.2 Removal of Sol-Gel Byproducts…………………………………..………………….131
4.3.6.3 Addition of GMA……………………………………………………………………131
4.3.6.4 Polymerization Step and Heating Treatment…………………………..……………..132
4.4 Results and Discussion………………………………………………………….……………134
4.4.1 Thermal Gravimetric Analysis (TGA)……………………………………………………134
4.4.2 Differential Scanning Calorimetry (DSC)………………………………………………..135
ix
4.4.3 Synthesis Considerations……………………………………………………………..…..135
4.4.4 Morphology and Transparency……………………………….…………………………..137
4.4.5 Mechanical Properties of PHGS hybrids……………………….………………………...138
4.5 Summary and Conclusion……………………………………………...……………………..140
4.6 Acknowledgements……………………………………………………..…………………….141
4.7 Reference List………………………………………………………………………………...157
Chapter 5. Capping of Hydroxyl Groups in Sol-Gel Materials
5.1 Introduction and Motivation………………………………………………………………….160
5.2 Experimental Part…………………………………………...……...…………………………162
5.2.1 Materials and Reagents…………………………………………...………………………162
5.2.2 Instrumentation…...………………………………………………...…………………….162
5.2.2.1 Near Infrared Spectroscopy (NIR)……………..……………………………………..162
5.2.2.2 Gel Permeation Chromatography (GPC)…………….…………….…………………162
5.2.2.3 Thermogravimetric Analysis (TGA)………………………………………………….163
5.2.3 Synthesis Procedure………………………………………………………………………163
5.2.3.1 GMA-Silica Hybrids……………………………………………………….…………163
5.2.3.2 GMA-HEMA-Silica Hybrids………………………………………………...……….164
5.3 Results and Discussion……………………………………………………………………….166
5.3.1 Shelf Life…………………………………………………………………………………166
5.3.2 Thermal Gravimetric Analysis (TGA)………………………………………………...….168
5.3.3 Near Infrared Spectroscopy (NIR)…………………….………………………………….170
5.3.4 Gel Permeation Chromatography (GPC)…………………………………………………171
5.3.5 Morphology…………………………...…………………………………………………..172
5.4 Conclusions…………………………….……………………………………………………..173
5.5 Acknowledgments…………………………...………………………………………………..173
5.6 Reference List………………………………………………………………………………...187
Chapter 6. Covalent Incorporation of Polyaniline in Sol-Gel Materials
6.1 Introduction and Motivation…………………………………………………………….……190
6.2 Experimental Section…………………………………………..……………………………..192
x